Nu-acylurethanes and their manufacture



Patented Dec. 29, 1942 xurt Engel, St. Louis, Ht. mun, France, and Kurt llaehler, Basel, Switzerland, assignors to the firm J. R. Geigy A. G., Basel, Switzerland No Draw ng. Original application July 1, 1938,

Serial do. 217,019.

Divided and this application July 28, 1939, Serial No. 287,180. In Switzerland July 12, 1937 .9 Claims.

This application is a division of our application Ser. No. 217,019, filed July 1, 1938.

According to the present invention a class of new, technically valuable compounds is obtained by treating urethanes of the formula fir-NH with fatty acids, their halides, esters and anhydrides to form substituted urethanes of the formula R1Nacyl In these formulae R1 means an aliphatic or hydroaromatic radical which may be substituted, R2 means an alkyl, aralkyl, cycloalkyl or aryl radical which may be substituted or not, and acyl means the radical of a saturated or unsaturated carboxylic acid, which may also contain heteroatoms or hetero-atom-groupings, such as O,'

S-, and which may further be substituted and especially may contain water-solubilizing groups or exchangeable halogen atoms.

For all three substituents, R1, R2 and acyl, the condition stands that at least one must be an aliphatic or alicyclic high molecular radical, i. e., must contain more than 8 carbon atoms.

The urethanes serving as primary materials are made in known manner, for instance from the carboxylic acid amides by Hofmann's decomposing process in alcoholic solution or from primary aliphatic or hydroaromatic amines by decomposition with appropriate carboxylic acid derivatives. As examples the following urethanes may be mentioned:

. Undecyl carbamic acid methyl-, ethyl-, propyl-, butyl amyl-ester, heptadecylcarbamic acid ethyl or amyl ester, urethanes respectively, made from the carboxylic acids of the naturally occurring or hydrogenated fats or oils, such as for example palm nut oil fatty acid, cocoanut oil N fatty acid, scyabean oil fatty acid, hydrogenated cod-liver oil fatty acid or fatty acids of resins or aliphatic compounds such as naphthenic acid, carboxylic acids of camphor, of fenchone, methyl carbamic acid methyl-, butyl-, decyl-, undecyl-,

f,dodecyl-, octodecyland oleic-ester.

Generally all halides, esters and'anhydrides of organic carboxylic acids are adapted for the acylation of the above named urethanes, such as for instance acetic, propionic, butyric, stearic, palmitic, phenoxyacetic, phenyl-amino vand thioacetic acid, dodecylthioacetic acid, octyl- ,thiopropionic acid and benzoic acid. The carboxylic acid derivatives with exchangeable halogen atoms have proved to be of special advantage, for instance the halides, anhydrides or esters of a-halogen fatty acids, such as the monoand dichloro-acetic acid, bromosucclnic acid, oz-bl'O- molauric acid; but aliphatic carboxylic acid derivatives, substituted in other positions by halogen or other organic carboxylic derivatives have also proved to be quite suitable. As examples 10 may be mentioned the chlorides of the benzylchloride-4-carboxylic acid, of the 2-chlorobenzoic acid and its substitution products, such as the 2-chloro-1-benzoic-5sulphonic acid.

The acylurethanes obtained with the abov mentioned halogenated carboxylic acid deriva tives can be used for numerous exchanging reactions due to the exchangeable halogen atoms. They may for instance be replaced by monovalent atom groupings, such as OR, SR, NRz,

R. generally meaning inorganic and organic substituents which may be the same or difierent (if two are present), as explained fully further on.

The group OR may be hydroxy, or the radicals of aliphatic, hydroaromatic, aliphatic-aromatic or'aromatic hydroxy compounds, such as of methyl-, ethyl-, benzyl-alcohol, cyclo-hexanol,

phenols. The organic hydroxy compounds are used in the best manner as alkali compounds for reaction. As examples for this sub-group of the new acylurethanes are named the reaction products of Nechloraceto-N-undecyl carbamic. acid methylester and sodium phenolate, of N-chloraceto-N-heptadecyl carbamic acid ethyl-ester and the monosodium salt of glycerol.

The group SR may be the inorganic radicals --SH, or radicals of mercaptans. These compounds can be made by decomposition of the halogen acyl urethanes with alkali-monoand '-poly,-sulphides or the alkali compounds of the v 1 mercaptans.

Of the latter compounds may be named for instance ethyl-, dodecyl-, phenyl-,

benzylmercaptan,-mercapto, acetic acid, a-mer- As examples for this sub-' capto benzthiazole. group are named the. reaction products of N- chloraceto-N iauryl carbamic acid methylester with sodium thiophenolate, sodium sulphhydrate. Finally, the group -NR2 may be a primary or secondary amino group. As examples of suit able N-compounds for the decomposition are named ammonia, monoand di-methyl;-- or -ethylamine, mono, or diethanolamine, amino..- acetic acid and derivatives, primary and second-' ary aromatic amines such as aniline and substi- I tution products, piperidine and so forth. As examples for this sub-group of the new acylurethanes are enumerated: the reaction products of N-chloraceto-N-heptadecyl carbamic acid alkylesters with dimethylamine, diethylamine and so forth.

molecular alcohols such as dimethylsulphate.

The new compounds, so far as they are insoluble'in water, may be used as softening agents and in the caoutchouc industry. The water soluble new compounds show in aqueous solution. distinct properties of capillary activity such as'a good foaming, wetting, dispersing and emulsifying power. Certain of the new compounds are also excellent softening agents for cellulose regenerate; Finally some of the new products may be used as bactericidal and fungicidial agents.

Generally the new acyl urethanes are made by reaction of urethanes in the presence of heat with fatty acid halides or halogen fatty acid halides, if necessary in presence of insert diluents, such as benzene, toluene, xylene. The acylation may also be carried out in presence of acid-binding agents, such as pyridine, diethylaniline etc.

Hereafter some explanatory examples of the process of the present invention are given, without limiting, however, the scope hereinbefore indicated, the parts being by weight.

Example 1 23 parts of undecylcarbamic acid methylester, made for instance by treating undecylamine with chlorocarbonic acid methylester by-known methd, are dissolved in 100 parts toluene, .19 parts of phenoxyacetic acid chloride are allowed to drop in while stirring and heating toboiling for 12 hours. After working up in known manner, the N-phenoxyaceto-N-undecylcarbamio acid meth-.

ylester is obtained in form of a semi-solid mass.

The reaction takes place according to the following formulaer CnHuNHrI-CIC 000K: CnHzaNllC OOCH3+HC1 C HnNlLC o 0 cm+otmo omo 0 01 1101+ O11H:aN.CO O CH:

oo.om.o.o.r'n The same compound is obtained by reaction of the N-chloraceto-N-undecylcarbamic acid meth ylester with phenol.

Example 2 23 parts of undecylcarbamic acid methylester are dissolved in 100 parts of toluene, 13 parts of chloracetic acid chloride are allowed to drop in whilst vigorously stirring and boiled for 12 hours.

The reaction takes place according to the following formulae: cum Nmo 0 o cm-i-oicoomoi 1101+ 0011,01 CnHn.N.C 0 0 on;

ocmooah Instead of the aforesaid undecyl-carbamic acid methylester, similar compounds may be used, for example the heptadecyl-carbamic acid ethylester, the undecyl-carbamic acid butylester, as ,acid chlorides for example butyric acid chloride; propionic acid chloride. The final products show similar properties.

Example 3 11 parts of mercapto benzene are dissolved in ,40 parts of alcohol and 4 parts of sodium hy- X=hydrocarbon-radical linked w i t h t h e -COOH-group in hydrogenated fish oil.

The same compound may also be made on starting with the phenylthioacetic acid chloride.

Example 4 50 parts of N-chloraceto-N-heptadecyl-carbamic acid methylester are allowed to drop into parts of an aqueous solution of dimethylamine of 20.4% strength. At the beginning the reaction mixture becomes slightly hot. Afterstirring for 24 hours at 60-70 C. the separated oil is isolated, if necessary by shaking out with ether.

15 parts of dimethyl sulphate are added to 38 parts of the obtained N-dimethylaminoaceto- N-heptadecyl carbamic acid methylester and heated for 12 hours on the water bath. A semisolid, wax-like mass is obtained being easily soluble in water, the solutions of which impart an excellent softness to regenerated and native cellulose.

The reaction takes place according to the following formulae:

ethyl esters or other compounds mentioned in the general description (page 1, sixth i) radicals connected with .the COOK-group in Examples 30 parts of N-chloraceto-N-heptadecyl carbamic acid methylester are heated with 30 parts of trimethylamine, used in form of an alcoholic solution of 33% strength, with 200 parts of ethyla-lcohol for hours in the autoclave at 130-140" C., then the alcohol and the excess of trimethyl-amine are distilled off. A brown waxlike mass is obtained which is clearly soluble in water. e

The reaction takes place according to the fol lowing formula: C 7II35.'N.CO0CHs+N(CHa)3 -vC 7H:5.N.C00CH3 OCH2.C1 (JIOCHzJT E(CH:):

In place of trimethylamine other tertiary amines maybe used, such as pyridine, nicotine. triethanolamine.

In place of'the reaction components used in the above examples, other possibilities of variation may be exercised in very great number by use of the particular compounds as mentioned above in the general description of the specification. There may only be named the reaction of methyl carbamic acid methylester with chlorides of higher fatty acids, such as oleic acid chloride, a bromolauric acid chloride; the resulting N-acyl-urethanes may be treated in the aforesaid manner, for example with ammonia derivatives and alkylated, if necessary.

What we claim is:

1. A process for the production of N-acylurethanes, comprising treating urethanes of the formula m-Nn wherein R1 means one of the group consisting 0 methyl, undecyl, heptadecyl, of the hydrocarbon radicals connected with the COOK-group in palm nut oil fatty acid, cocoanut oil fatty acid, soyabean oil fatty acid, hydrogenated cod-liver oil fatty acid, resin ,acid, naphthenic acid, camphor carboxylic acid and fenchone carboxylic acid and R2 means one of the group consisting of alkyl, benzyl, cycloalkyl and phenyl radicals, with acylating agents to form the N-acylurethanes of the following formula:

methyl, undecyl, heptadecyl, of the hydrocarbon palm nut oil fatty acid, cocoanut oil fatty acid, soyabean oil fatty acid, hydrogenated cod-liver oil fatty acid, resin acid, naphthenic acid, camphor carboxylic acid and fenchone carboxylic acid and Rs means one of the group consisting of alkyl, benzyi, cycloalkyl and phenylradicals. wherein acyl means the acyl radical of a carboxylic acid, whereby at least one of the groups R1 and R: must be one of the group consisting of alkyl and cycloalkyl radicals containing more than 8 carbon atoms, said products being valuable assistants for the textile and related industries. h 4. N-acylurethanes according to claim 3, whose acyl radicals contain a substituent with a quaternary nitrogen atom. a 5. N-acylurethanes of the following formula Higher alkylNCO.CHr-X 0 0 .lower alkyl wherein higher alkyl means an alkyl radical having more than 8 carbon atoms and lower alkyl means an alkyl radical with a carbon atom number lower than 8, x being a quaternaryamino group.

6. N-acylurethanes of the following formula Lower alkykN-C 0 CH -X 0O.higher alkyl wherein higher alkyl means an alkyl radical having more than 8 carbon atoms and lower alkyl means an alkyl radical with a carbon atom numher lower than 8, X being a quaternary-amino group '7. The acylurethane of the following formula CnHu-N-C 0.0H:N\

AOOCII;

being a semi-solid wax-like mass, easily soluble in water, the solutions of which possess remarkable bactericidal and fungicidal properties.

8. The acylurethaneof the following formula Cl CH: CuHrr-N-C O.CHg-N C O O .CHs l CH1 HaCsHI being a semi-solid wax-like mass, easily soluble in water, the solutions of which possess remarkable bactericidal and fungicidal properties 9. The acylurethane of the following formula being a semi solld wax-like mass, easily soluble in water, the solutions of. which impart an excellent softness to regenerated and native cel lulose- KURT ENGEL.

KURT PI'AEHLER. 

